Palladium (Pd) and gold (Au) are the most often used precious metals (PMs) in industrial catalysis and electronics. Green recycling of Pd and Au is crucial and difficult. Here, we report a peroxydisulfate (PDS)-based advanced oxidation process (AOPs) for selectively recovering Pd and Au from spent catalysts. The PDS/NaCl photochemical system achieves complete dissolution of Pd and Au. By introducing Fe(II), the PDS/FeCl2<middle dot>4H(2)O solution functioned as Fenton-like system, enhancing the leaching efficiency without xenon (Xe) lamp irradiation. Electron paramagnetic resonance (EPR), O-18 isotope tracing experiments, and density functional theory calculations revealed that the reactive oxidation species of SO4<middle dot>(-), <middle dot>OH, and Fe(IV)& boxH;O were responsible for the oxidative dissolution process. Lixiviant leaching and one-step electrodeposition recovered high-purity Pd and Au. Strong acids, poisonous cyanide, and volatile organic solvents were not used during the whole recovery, which enables an efficient and sustainable precious metal recovery approach and encourage AOP technology for secondary resource recycling.